Processes for breaking petroleum emulsions



Patented Sept. 18, 1951 UNITED STATES PATENT O -me PROCESSES FQRBREAKINGPETROLEUM EMULSION S Melvin De Greats;- Uiiiversity City, and BernhardKeiser, Webster Graves, M6;,-as'signors to Petrolite Corporation, Ltd.,Wilmington, Del., a corporation of Delaware i do firming. i A pplication January 6; 1950, Sfiall N0. 137,294

5 Claims; (01. 252 331l,

This invention relates to processes or pm Thepresent process iseencerhezi-wiai lirali cedures particularly adapted 'for preventing,petroleum-emulsions of the esteem-simple? breaking, orresolvingemulsions of the water-' characterized by subjecting theemulate-ts the in oil type, and particularly petroleum emul= actiori ofa'deiriiilsi'fir; including hi' dr'ofah e sions. This application is acontinuation-in 5 synthetic products; said hydroph'ile'sy'r'flil'ietipart of our cd-pencling application Serial No; reduetstem oxyalkylatidii product's of--'--' 8,723, filed- February l6, I948whichrh'a'snowmw (A A11 alphafldeta alkyl'eh' Ofiide having not tu'redinto Patent NO. 2,499,366; dated March 7,. more than when atif1s' af1dselected from the 1950. Alsosee ourco-p'ending application Serial classconsisting of ethylene oxide; propylene No. 74,474, filed February 3',-1949'; ojiide butylehe oiiid; glyci d andriiethylglycide;

Complementary to the above aspect of the and invention is our companioninvention concerned (-3) oxyallylation susceptible; fusible;- with thenew chemical" products" or compounds cream 'sol-vent-"soli1lole',- waterinsoluble phenol used as the demulsifying agents in said aforefurfiiralresin; said resin being derived by rac mentioned processesv or procedures, as well as tion between" a clifuncti'onal' m'onohydr'icp'heiiol" the application oi sucli' chemical compounds, and'fur'fiiral;said'resin being formed in thesiibproducts, and the like, in variousother arts and stantial' absence of trifun'ctionalphenols, saidindustries, along with the riiethodifor m'a-nu phenolbeing' of theformula: facturing said new chemical products or com- V 1. pounds whichare of outstanding value in de v 7 F mulsification. See our co-pendingapplication Serial No. 137,295, filed January 6, 1950.

Our invention provides an economical and rapid process for resolving--petroleum emulsions of the water-=in-oil type, that are commonly r eetm,and which comprise fine droplets of 9 K i tt fil E39 a ?..,9e 9P. q inaturally-occurring waters or brines dispersed PP c J I H EQ i 9 a i fix'1 in a more or less permanent state throughout the; 1? ,rm t f e 9 3% T9F A tni I oil which constitutes the continuous phase of 3 9: 9-, l aPlllralllpy the emulsion. alet ete isaelslher eefih y It also providesan economical and rapid proc- WFQP; V3 Q 3]??? a u t 199 i ess forseparating emulsions which have been conslstlnggof e'thylene radlqalslpropylem? K i prepared under controlled conditions from min- 3 bu y gpaq g h m sypr yl 1 N eral oil, such as crude oil and relatively soft aiP 39.BXQ PWE XE Q, d ala aqq n, 1 waters or weak mines. Controllediiiuls'ificanyme aL yiagjr9 F9 Q: }3 3 s $9 tion and subsequentdemusifieacdn under the hatatlse i ifeltiii q i9 x1de be conditionsjiistmefitioned"are or signifieenwame" usslfilfief? cl l fcl l flll fi ue e vA s c m remofing impurities, particularly inorganic" For purpose ofconvemence, What IS salts, frompipelirie oil; v I I Demulsifi cation; ascontemplated thepr'esf ent application, includes the preventative stepof commingling the demulsifier with the aqueous v component which wouldor might subsequently fl a if L- become either phase of the emulsion inthe aba hydrophfle I ma "at 711. $1.. an a s'eii'ceof such preeaumonafymeasure.- Similarly. droxylated lv lv n Part 3 W111 be con suchderhiilsifier maybe mixed" with the hydro cerned With the e 9i suqh e alv s as d mulcarbon component. sifiers, as hereinafter" described.

Briefly stated, the present process is coil; PART 1 cerned withthejbreaking of resolving-of petrov i y Ieum emulsions liy'means'oftlieoxyalkylate'd-de' The production of resins from difunct-ional: rivatives(if certain resins" hereinafter specified;- hydrocarbon-substitutedphenols wellknown and such resins are important in the art, particularlyin the preparation of varnish and similar coatings. Those derived fromfurfural instead of formaldehyde, for example, have limitations in theiruse, due to the fact that furfural is apt to give a compound having adark color. In any event, the production of such resins is conventional.

In the preparation of the resins and also in the subsequentoxyalkylation step described in Part Two, frequent reference will bemade to a number of co-pending applications, for purpose of reference asrequired.

Example 1AA Grams Para-tertiary amylphenol 1s.... 164 Furfural 96Potassium carbonate 8 The equipment used was a conventional two piecelaboratory resin pot. The cover part of the equipment had four openings;one for reflux condenser, one for the stirring device, one for aseparatory funnel or other means of adding reactants; and a thermometerwell. The device was equipped with a combination reflux and water-trapapparatus, so that the single piece of apparatus could be used as eithera reflux condenser or a water trap, depending upon the position of thethree-way glass stop-cock. This permitted convenient withdrawal of waterfrom the water trap. The equipment, furthermore, permitted any settingof the valve without disconnecting the equipment. The resin pot washeated with a glass fibre electrical heater constructed to. fitsnuglyaround the resin pot. Such heaters, with regulators, are readilyavailable.

- The furfural was shaken with dry sodium carbonate prior to use, toeliminateany acid, etc. The procedure employed was substantially thatdescribed in detail in Technical Bulletin No. 109 of the Quaker OatsCompany, Chicago, Illinois. The above reactants were heated under thereflux condenser for two hours in the same resin pot arrangementdescribed above. As previously stated, the separatory funnel device wasnot employed. No xylene or other solvent was added. {The amount ofmaterial vaporized and condensed was comparatively small, except for thewater of reaction. At the end of this heating or reflux period the trapwas set to remove the water. The maximum temperature during and afterremoval of water was approximately 202 C, The material in the traprepresented 16 cc. water and 1.5 cc. furfural. The resin was a brightblack, hard resin, xylene-soluble, and had a melting point of 180 to 135C., with some tendency towards being slowly curable. We have alsosuccessfully followed this same procedure,

using 3.2 grams of potassium carbonate instead Example 2.4.4

7 Grams Para-tertiary amylphenol 164 Furfural-(carbonate treated) -70Potassium carbonate 3. 2

Example 3AA Grams Nonylphenol (1.0 mole) 220 Furfural (NazCO; treated)(1.0 mole) 96 Potassium carbonate 12 Xylene 200 The furfural was shakenwith dry sodium car bonate prior to use to eliminate any acids,'ete.-,as in previous examples. The procedure em ployed was substantially thatdescribed in detail in Technical Bulletin No. 109 of the Quaker OatsCompany, Chicago,'Illinois. The materials, except the xylene, wereheated under a reflux condenser for 2 hours in the same resin potarrangement described in Example 1AA. At the end of this heating orreflux period the trap was set to remove the water, and the xylene addedafter most of the water had distilled. The maximum temperature duringand after removal of water was approximately 205 C. The resin was areddish black resin, xylene-soluble, and semi-soft to pliable inconsistency.

See Example a of our co-pending application Serial No. 8,723, filedFebruary 16, 1948, or Example 880. of Serial No. 74,474, filed February3, 1949.

Example 4AA Grams Menthylphenol (1.0 mole) 232 Furfural (NazCOa treated)(1.0 mole) 96 Potassium carbonate 12 Xylene 200 The same procedure wasfollowed as in Example 1AA, preceding, except that 206 parts by weightof commercial para-octylphenol replaced 164 parts by weight ofpara-tertiary amylphenol. In co-pending application Serial No. 74,474this particular resin is indicated as Example 144a, and the resinpreviously referred to as Example 1AA is referred to as Example 42a.

Example 6AA The same procedure was followed as in Example lAA,preceding, except that parts by weight of commercial para-phenylphenolreplaced 164 parts by weight of para-tertiary amylphenol. Inour'co-pending application Serial .No.

Example 7AA Grams Para-tertiary butylphenol 150 Furfural, (NazCOstreated)" 96 Iotassium carbonate Xylene 200 The procedure employed wasthe same as that in Example 1AA, preceding. The solvent-free resin wasblack or reddish black in color, xylenesoluble, hard and very brittle.Its melting point was between 220-230 C. It was found to beheat-curable.

Example 8AA This resin was made in exactly the same way as Example 1AA,except that 164 parts by weight of para-tertiary amylphenol werereplaced by 206 parts by weight of para-octylphenol. The final producthad substantially the same appearance,

solubility characteristics, etc., as resin Example 1AA.

Example 9AA This resin was made in exactly the same way I as Example1AA, except that 164 parts by weight of para-tertiary amylphenol werereplaced by 170 parts of commercial para-phenylphenol. The final producthad substantially the same appearance, solubility characteristics, etc.,as resin Example lAA. I

The resinification procedure previously I described yields resins havingat least 3 phenolic nuclei and usually modestly in excess thereof. In

other words, an average of 4, 5 or 5 /2 or 6 nuclei per resin molecule.

As pointed out in our aforementioned co-pending application Serial No.8,723, other means are available to yield resins in which there may bepresent a larger number of phenolic nuclei, for

PART 2 Example 1BB The resin employed was the one described under theheading of Example 1AA. 100 grams of the resin were mixed with 100 gramsof xylene so as to give a solution. 2% of sodium methylate, based on thesolvent-free resin, was added as a catalyst. The solution of the resinwas placed in a small laboratory autoclave and the mixture reacted with50 grams of ethylene oxide. During this addition the maximum temperaturewas 115 0., the maximum pressure was 1051 pounds per square inch, andthe time required to add the oxide was 2 hours. Needless to say, themixture was stirred constantly during the reaction and the reactionconsidered at an end when there was no further drop in pressure, thusindicating that all the ethylene oxide present had reacted. The pressureregistered on the gauge at the end of the reaction indicated the vaporpressure of xylene at the indicated temperature. At the end of thisfirst addition there was no particular change in the solubility of thproduct, i. e., it was practically as insoluble as the original xylenesolution of the resin. A sec ond 50 grams of ethylene oxide were addedin another 2-hour period. In this second addition the maximumtemperature was 130 and the maximum pressure pounds. At the end of thisperiod the product began to show a definite tendency to emulsify.

A third 50-gram addition of ethylene oxide was then made during aone-hour period. In this particular addition the maximum temperature wasand the maximum pressure 96 pounds. The product at the end of this3-hour period was entirely water-soluble.

Example 2BB The same procedure was followed as in Example lBBimmediately preceding, except that the resin employed was that oiExample 2AA, instead of 1AA. The two initial resins were very much alikeand the conditions of addition were substantially the same, i. e., gramsof ethylene oxide added to 100 grams of resin in three periods of 2hours, 2 hours and 1 hour. The conditions under which additionofethylene oxide was made, as far as temperature and pressure areconcerned, were substantially the same as in Example 133, preceding. Theamount of sodium methylate added was the same, and the solubilitycharacteristics at the end of each period were substantially the same.

Example 3BB The same reactants, and procedure were employed as inExample lBB, preceding, except that propylene oxide was employed insteadof ethylene oxide. The resultant, even on the addition of the alkyleneoxide in the weight proportions of the previous example, has diminishedhydrophile properties, in comparison with the resultants of Example113B. This illustrates the point that propylene oxide and butylene oxidegive products of lower levels of hydrophile properties than doesethylene oxide.

Example 4BB The same reactants and procedure were followed as in ExamplelBB, preceding, except that one mole of glycide was employed initiallyper hydroxyl radical. This particular reaction was conducted withextreme care and the glycide was added in small amounts representingfractions of a mole. Ethylene oxide was then added, following theprocedure of Example lBB, to produce products of greater hydrophileproperties. We are extremely hesitant to suggest even the experimentaluse of glycide and methylglycide for the reason that disastrous resultsmay be obtained even in experimentation with laboratory quantities.

Example 5BB The same procedure was followed as in Example lBB,preceding, except that the resin employed was the one described underthe heading of Example 7AA. The amount of resin used was 100 grams,dissolved in grams of xylene. 4 grams of sodium methylate were added,along with 100 grams of ethylene oxide. Due to the increased amount ofcatalyst, the reaction time was somewhat more rapid thanjn Example 1AA,

7 preceding. The reaction was complete in onehalf hour. The maximumtemperature employed was 150 C., and the maximum pressure 150 pounds persquare inch. At the end of this period'the product showed some tendencyto emulsify. T

- The second addition of 100 grams of ethylene oxide was then made. Thetime required was 1 hours, the maximum temperature was 150 C., and themaximum pressure 160 pounds.

The product showed definite water-emulsifiability but was notwater-soluble.

A third addition of ethylene oxide was made,

using another 100 grams. The maximum temperature during this period was162 C., and the maximum pressure 165 pounds. The time required was 2%hours. During this third period there was a definite tendency towardrubberiness and the product seemed to be only partially soluble inxylene. The product was solubilized by the addition of the diethyletherof ethylene glycol. 150 grams of this solvent were added. The productthen was a deep amber-colored, somewhat viscous liquid, which waswater-soluble.

' Instead of preparing resins on a laboratory scale, we have alsoprepared phenol-furfural resins of the kind described, in a 10 tol-gallon electro-vapor synthetic resin pilot plant reactor. Such pieceof equipment is manufactured by the Blaw-Knox Company, Pittsburgh,Pennsylvania, and is described completely in their Bulletin No. 2087,issued in 1947, with specific reference to Specification No. 7113,965.

For convenience, the numbers given in the following tables are the sameas the identical laboratory size batches previously described, and it isunderstood that they were simply stepped Phenol for resin: Para-tertiaryamylphenol Date, August 27-31, 1948 up in size, but otherwise made inthe pilot plant equipment previously described.

The solvent used in each instance was xylene. This solvent isparticularly satisfactory, for the reason that it can be removed readilyby distil lation or vacuum distillation. In these continuous experimentsthe speed of the stirrer in the autoclave was 250 R. P. M.

In the subsequent tables it will be noted that if a comparatively smallsample is taken at each stage, for instance, one-half to one gallon, onecan proceed through the entire molal stage of one to one, to one to 20,without remaking at any intermediate stage. However, in most cases, wehave found it desirable to take a larger sample, for instance, a3-gallon sample, at an intermediate stage. As a result, it was necessaryin such instances to start with a new resin sample, in order to preparesuflicient oxyethylated .derivatives illustrating the latter stages.Under such circumstances, of course, the earlier stages which had beenpreviously prepared were by-passed or ignored. This is illustrated inthe tables, where obviously, it shows that the starting mix was notremoved from a previous sample. Such pilot plant size resin pot isadapted to operate under pressure; and provided the resin permits awork'- ing pressure of 200 pounds or thereabouts, resinification andoxyalkylation can take place in the same piece of equipment. We haverepeatedly used equipment for this dual purpose.

In order to do what we have stated previously, i. e., preserve referenceto our copending application Serial No. 74,474, filed February 3, 1949,we are presenting the same data which appears therein in verbatim formadding only one thing to identify the resin in the instant case.

Aldehyde for resin: Furfural [Resin made on pilot plant size batch,approximately 25 pounds, corresponding to 42a but this batch designatedas 1340].

Mix at End of Starting Mix Reaction Mix Which is Removed for Sample MixWhich Remains as next Starter Max. Max.

Resin 1AA Lbs. Solvent Lbs. Res- Lbs. Solvent Lbs. Resin Lbs. SolventLbs . Lbs. EtO

EtO in Lbs. Res- Lbs. EtO

Pressure Time, lbs. sq. in.

Tempera- Solubility ture, C.

Lbs. S01- vent Lbs. Resin Lbs. EtO

Ez.'6BB First Stage Resin to Et0... Molal Ratio 1:1. Ex.No.134b.....

Er. 'lBB Second Stage Resin to EtO.... Moial Ratio 1:5.. Ex. No. 1350E2. 8138 Third Stage Resin to EtO Molal Ratio 1:10. Ex. No. 1365.....

E1. 912B Fourth Stage Resin to Et0.... Molal Ratio 1:15. Ex. No.1371).....

Ex. 10B]? Fifth Stage Resin to EtO.. Molal Ratio 1:20. EX.N0.138)....

8. 45 13. 6 2. 65 Not soluble.

Somewhat soluble.

2.05 3.65 6.60 163 Soluble.

Very soluble.

Resin is 1 1.4. Refe ence to 42a and 1340 is for comparison with to Ex.1340 to 138b, inclusive. These 5 examples in the present case Serial No.74,474,'fi1ed Feb. 3, 1949. This is true also in regard are, as noted,Examples 6138 thru 10BB, inclusive.

to reference -2, .6B,1 1. 9 310 Phenol for resin: Para-.nonylphenal'Aldehyde for resin: Fwrfural Date, October 13-15, 1948 [Resin made onpilot plant size batch, approximately 25 pounds, corresponding to 8811but this batch designated as 154a].

. Mix Which is Mix Which Re- Starting Mix aggi of Removed for mains asnext Sample Starter Max Pressure Tempsra- 13? Solubility Lbs. Lbs. LbLbs. Lbs. Tb Lbs. Lbs. Tb Lbs. Lbs. Lb So1- Resa Sol- Res- Sol- Res-Sol- Resvent in vent in vent in vent in Resin 3AA E1. 1 1 BB First StageResin to EtO.... Molal Ratio 1:1 85 Ex. No. 1545...

E1. 1213B Second Stage Slight Resin to EtO.

2o. 75 10.85 20. 75 3.0 2.57 4.90 0.73 8.28 15.85 2.27 100 150 15Insoluble.

tendency Molal Ratio 1:5.. 15. 85 2. 27 8. 28 15.85 11. 77 3. 82 7. 335.45 4. 46 8. 52 6.32 100 182 }6 toward Ex. No. 1555..." becomingsoluble. E1. 1388 Third Stage Resin to EtO. Molal Ratio 1:10. 5 95Ex.No.156b.....

E1. 1419B Fourth Stage Resin to EtO. Molal Ratio 1:15. 4.46 Ex. No.1571).....

E1. 1533 Fifth Stage Resin to EtO..-.

8 2 6.32 4.46 8.52 19.07 "I 90 188 Readily soluble.

Molal Ratio 1:20.

4.93 7.25 2.57 4.93 14.50 Ex.No.158b...-.

r 100 150 5 s Quitesoluble.

Resin is 3AA. Reference 08811 and 154a is for comparison with Serial No.74,474, filed Feb. 3, 1949.. This is true also in regard to reference toEx. 15411 to 1585. inclusive. These 5 examples in the present case are,as noted, Examples 1113B tliru 1513B, inclusive. 1

Phenol for resin: M enthyl phenol Aldehyde for resin: Fw'fural Date,September 23-24, 1948 [Resin made on pilot plant size-batch,approximately pounqls, corresponding to 89-1but this batch designated as1390.]

- Mix Which is Mix Which Re- Mlfiat 5 Removed for mains as next e SampleStarter Starting Mix Max. Max. gressu e em g'gture Lbs. Lbs. Lbs. Lbs.Lbs. Lbs. Lbs. Lbs. 1

' Lbs. Lbs. Lbs. Lbs.

S0l- Res- 801- Res- 1 S01- Res- Sol- Res- 1 vent in Eto vent in m0 ventin Em vent in Eto hrs.

Solubility Er. 1688 First Stage Resin to EtO.. M0181 Ratio 121.. 10.25Ex.No.139b.

Ex. 1712B Second Stage Resin t0 EtO....

17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 150 Not Soluble.

Molal Ratio 1:5. Ex. No.140b.....

E1. 183B Third Stage Resin to EtO.

Somewhat soluble.

Mnlal Ratio 1:10. Ex. N0. 1411).....

E1. 19B Fourth Stage Resin to EtO.

6. 98 4. 22 6. 98 10. 0 165 )5 Soluble.

Molal Ratio 1:15. Ex. No. 14211"...

Er. ZOBB F1 fth Stage Resin to EtO...

3.75 5.241525 171 tg Verysoluble.

M011] Ratio 1:20. Ex. N 1435.

4.15 2.95 2.4 4.151170. 90 tsvqr solubie'.

Resin is 4AA. Reference to 89a and 139;: is for comparison with Serial N0. 74,474, filed Feb. 3, 1949. This is true also in regard to referenceto Ex. 1395 to 1431), inclusive. These 5 examples in the present caseare, as noted, Examples [BBB through 'ZO'BB. inclusive.

1.1.35 5.95 11.35 16. 75 3. 38 6.42 9.50 2. 57 4. 93 7.25 100 181Fairly-Soluble.

Phenol for resin: Paraoctyl Phenol Aldehyde'for resin: 'Furfural Date,October 7-8, 1948 Resin made on pilot plant size batch, approximately 25pounds, corresponding to 42a with 206 parts by weight of commercialpa-ra-octylphenol replacing 164 parts by weight of para-tertiaryarnylphenol but this batch designated as 144.1]

. Mix Which is 6 Mix Which Re.- Starting Mix fig; 3 of Removed for mainsas next Sample Starter v I Max. Max. Time Resin 8AA Pressure TempcrahrsSolubility Lbs. Lbs. Lbs Lbs. Lbs. I M Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol-Res- Sol- Resfi Sol- Rcs- Sol- Resb' vent in vent in vent in vent in E1.213B First Stage Resin to EtO. Molal RatiO 111.. 12. 1 18. 6 12. 1 18. 63.0 5. 38 8. 2S 1. 34 6. 72 10. 32 1. 66 80 150 M2 Insoluble. Ex. N0.1446.

Er. 223B Second Stage Slight Resin to EtO v tendency Molal Ratio 115" 925 14. 25 9. 25 14.25 11.0 3.73 5.73 4.44 5. 52 8. 52 6. 56 100 177 i:toward Ex. No. 145'). becoming soluble.

Er. 23B]? Third Stage Resin to Et0 s Faifl Molal Ratio 1:10. 6.72 10.321.66 6.72 10.32 14.91 4.97 7.62 11.01 1.75 2.70 3.90 85 182 A solublserEx. No. 1466... v

Ex. 24BB Fourth Stage Resinto EtO.... Molal Ratio 1:15.} 5. 52 s. 526.56 s. 52 8.52 19.81 100 176 ,5 gfig g' Ex. No.147b.

E1. 26BB Fifth Stage Resin toEtO. Quite M01911 Ratio 1:20- 1 75 2. 703.90 1. 75 2. 70 8. 4 80 160 M soluble Ex. N0. 1481).-.

Resin is 8AA. Reference to 42a and 144a is for comparison with SerialNo. 74,474, filed Feb. 3,1949. This is true also in regard to referenceto Ex. 144b through 1486, inclusive. These 5 examples ll'l thepresentcase are, as noted, Examples 21BB thru BB, inclusive.

Phenol for resin: Para-phenytphenol- Aldehyde for resin: Furfural Date,October 11-13, 1948 [Resin made on pilot plant sizebatch, approximately25 pounds, corresponding to 42a with 170 parts by weight of commercialparaphenylphenol replacing 164 parts by weight ofpara-tertiary-amylphennl but this batch designated as-14911.]

- Mix Which is Mix Which Refizg g gg of Removed for mains as Next 7 mmMax .Max.

' llgressure, Ternpggafig Solubility Sol- R es- 55% 801- Res- $5 801-Resg gg- Sol- Res- E 8 vent in H vent in vent in vent in Starting MixResin 9AA Ex. 268B First Stage Resin to EtO Molal Ratio 1:1 13 9 16. 713. 9 16. 7 3. 0 3. 50 4. 25 0.80 10.35 12. 45 2. 20 100 160 AInsoluble.

Ex.No.149b....:

E1. 2733 Second Stage Resin to EtO Slight IA tendency toward solubility.

M0131 Ratio 1:5. 12.45 2.20 10.35 12. 12.20 5.15 6.19 6.06 5.20 6.266.14 183 E17. 283B Third Stage 1 26519236 Fairly 0 a atiO 8. 10. 7 8. 9010. 70 19. 0 5. 30 6.38 11. 32 3. 60 4. 32 7. 68 90 193 16 Ex. No.1516... soluble.

Er. 29BB Fourth Stage Resm to EtO 5. 20 Readily M0131 Ratio 1:15.soluble.

EX. N0. 1521)- Er. SOBB Fifth Stage Resin to EtO 4.32 7. 68 3.60 4.3215.68 Sample somewhat rubbery and ge- 230 2 latinous but fairly solubleMolal Ratio 1:20. Ex. No.153b

Resin is 9AA. Reference to 42a and 149a is for comparison with SerialNo. 74,474, filed Feb. 3. 1949. This is true also in regard to referenceo Ex. 149!) to 153b, incluslve. These 5 examples in the present mse are.as noted, ExamplesZGBB thru BOBB, inclusive.

water-in-oil emulsion or an oil-in-water-emulsion depending upon theratio of the-two phases, degree of agitation, concentration ofemulsifying agent, etc.

' The same is true in regard to the oxyalkylated resins hereinspecified, particularly in the lower stage of oxyalkylati'on, theso-called sub-surfaceactive stage. The surface-active properties arereadily demonstrated by producing a xylene-water emulsion. A suitableprocedure is as follows: The oxyalkylated resin is dissolved in anequalweight of xylene. Such 50-50 solution is then mixed with 1-3 volumes ofwater and shaken to produce an emulsion. The amount of xylene isinvariably suflicient to reduce even a tacky resinous product to asolution which is readily dispersible. The emulsions so produced areusually xylene-in-water emulsions (oil-in-water type) particularly whenthe amount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awater-in-xylene emulsion (water-in-oil type) .which is apt to reverse onmore vigorous shaking and further dilution with water. i

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followedby oxyalkylationusing'2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 /2 units per resin molecule. Such resin, when diluted with anequal weight of xylene, will serve to illustrate the aboveemulsification test.

In a few instances, the resin may not sufiiciently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposef this test. r

In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used inaccordance with this invention. They dissolve'or disperse in water; andsuch dispersions foam readily.

With borderline cases, i. e., those which show "only incipienthydrophile 'or surface-active property (sub-surface-activity) tests foremulsifying properties or self-dispersibility are useful. The fact thata reagent is capable of producing a dis pers'ion in water is proof thatitiis distinctly hydrophile. In doubtful cases, comparison can be madewith the butylphenol-formaldehyde resin analog wherein 2 moles ofethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, hit is desirable todetermine the approximate point where self-emulsification begins, thenit is better to eliminate the xylene or equivalent from a small portionof the reaction mixture and test such portion. In some cases, suchxylene-free resultant may show initial or incipient hydrophileproperties, whereas in. presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene.

It is to be emphasized that hydrophile properties herein referred to aresuch as those exhibited by incipient self-emulsification or'the presenceof emulsifying properties and go through the range of homogeneousdispersibility or admixture with water even in presence of addedwater-insoluble solvent and minor proportions of common electrolytes asoccur in oil field brines.

Elsewhere, it is pointed out that an emulsifica tion test may be used todetermine ranges of sur-' face-activity and that such emulsificationtests employ a xylene solution. Stated another way, it is reallyimmaterial whether a xylene solution produces a sol-or whether it merelyproduces an emulsion. 1

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the effectiveness of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophilecharacter, it become obvious that there is a wide variation in theamount of alkylene oxide employed, as long as it is at least 2 moles perphenolic nucleus,for producing products useful for the practice of thisinvention. Another variation is the molecular size of the resin chainresulting from reaction between the difunctional phenol and the'aldehydesuch as formaldehyde. It is well known that the size and nature ofstructure of the resin polymer obtained varies somewhat with theconditions of reaction, the proportions of reactants, the nature of thecatalyst, etc.

PART 3 Conventional demulsifying agents employed in the treatment of oilfield emulsions are used as such, or after dilution with any suitablesolvent, such as water, petroleum hydrocarbons, such as benzene,toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols,particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octylalcohol, etc., may be employed as diluents. Miscellaneous solvents, suchas pine oil, carbon tetrachloride, sulfur dioxide extract obtained inthe refining of petroleum, etc., may be employed as diluents. Similarly,the material or materials employed as the demulsifying agent of ourprocess may be admixed with one or more of the solvents customarily usedin connection with conventional demulsifying agents. Moreover, saidmaterial or materials may be used alone, or in admixture with othersuitable well-known classes of clemulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form or in an oil-soluble form, or in a form exhibitingboth oiland water-solubility. Sometimes they may be used in a form whichexhibits relatively limited'oil-solubility. However, since such reagentsare frequently used in a ratio of 1 to 10,000, or 1 to 20,000,or 1 to30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice,such an apparent insolubility in oil and water is not significant,because said reagents undoubtedly have solubility within suchconcentrations. This same fact is true in regard to the material ormaterials employed as the demulsifying agent of our process.

In practising our process for resolving petroleum emulsions of thewater-in-oil type, a treating agent or demulsifying agent of the kindabove described is brought into contact with or caused to act upon theemulsion to be treated, in any of the'various apparatus now generallyused to resolve or break petroleum emulsions with a chemical reagent,the-above-procedure being used alone or in combination with otherdemulsif-ying procedure, such as the electrical dehydrationzprocess.

One type of-procedure is toaccumulate a volume of emulsified-oil in atank and conduct a batch treatment ;type of demulsification procedure torecover clean oil. In this procedure the emulsion is admixed with thedemulsifier, for example by agitating the=tankof emulsion and slowlydripping demulsifier into the emulsion. In "some cases mixing -is'achieved by heating the emulsion while dripping in the demulsifier,depending upon the convection currents in the emulsion to producesatisfactory admixture. Ina third modification of this type oftreatment, a circulating pump=witndraws emulsion from, e. g., the bottomof the tank, and re-introduces it into the top of the tank,thedemulsifier being added, for example, at the suction side of saidcirculating pump.

In a second type of treating procedure, the demulsifier is introducedinto the well fluids at the well-head or at some point between thewell-head "and the final oil storage tank, bymeans ofan'adjustableproportioning mechanism 'or proportioning pump. Ordinarily the "flow offluids through "the subsequent lines and fittings-suffices to producethe desired degree of mixing of demulsifier and emulsion, although insome instances additional mixing devices may be introduced into the flowsystem. In this general procedure, the system may include variousmechanical devices for withdrawing free water, separating entrainedwater, or accomplishing quiescent settling of the chemicalized emulsion.Heating devices may likewise be incorporated in any of the treatingprocedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsionis to introduce the demulsifier either periodically or continuously indiluted or undiluted form into the well and to allow it to come to thesurface with the well fluids, and then to flow the chemicalized emulsionthrough any desirable surface equipment, such as employed in the othertreating procedures. This particular type of application is decidedlyuseful when the demulsifier is used in connection with acidification ofcalcareous oil-bearing strata, especially if suspended in or dissolvedin the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, thebroad process consists simply in introducing a relatively smallproportion of demulsifier into a relatively large proportion ofemulsion, admixing the chemical and emulsion either through natural flowor through special apparatus, with or without the application of heat,and allowing the mixture to stand quiescent until the undesirable watercontent of the emulsion separates and settles from the mass.

The following is a typical installation:

A reservoir to hold the demulsifier of the kind described. (diluted orundiluted) is placed at the well-head Where the efiluent liquids leavethe well. This reservoir or container, which may vary from 5 gallons to50 gallons for convenience, is connected to a proportioning pump whichinjects the demulsifier drop-wise into the fluids leaving the well. Suchchemicalized fluids pass through the flowline into a settling tank. Thesettling tank consists of a tank of any convenient size, for instance,one which will hold amounts of fluid produced in 4 to 24 hours (500barrels to 2000 barrels capacity), and in which there is a perpendicularconduit from the top of the tank to .pipeline or dehydrated oil. Ifdesired-the conduit or pipe which serves to carry-thefluidsfrom the wellto the settling tankcmay include a sectionof pipe withbaflles tooserveas a mixer, to insure thorough distributionofthe demulsifier through.-out the fluids, or a heater for raising the temperature of the fluids tosome convenient temperature, for instance, to F., or both heater andmixer.

Demulsification procedure is started by simply setting the pump so as tofeed a comparativel As soonas a complete ""breaik-orsatisiactorydemulsification is obtained; the pump is regulated untilexperience show'sjthat the amount of *declean or "dehydrated -oi l. 'Thamourit bei11g fed at such stage is usually 1:10,000, 1:15,000, 120,000,or the like.

In many instances the oxyalkylated products herein specified asdemulsifiers can be conveniently used without dilution. However, aspreviously noted, they may be diluted as desired with any suitablesolvent.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifier,including hydrophile synthetic products; said hydrophile syntheticproducts being oxyalkylation products of (A) an alpha-beta alkyleneoxide having not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycideand methylglycide; and (B) an oxyalkylation-susceptible, fusible,organic solvent-soluble, waterinsoluble, low-stage phenol-furfuralresin; said resin being derived by reaction between a difunctionalmonohydric phenol and furfural; said resin being formed in thesubstantial absence of trifunctional phenols; said phenol being of theformula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R10) n in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral vary ing from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the final proviso that the hydrophileproperties of said oxyalkylated resin in an equal weight of xylene aresuflicient to' produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of vent-soluble, water-insoluble,low-stage phenolfurtural resin; said resin being derived by reactionbetween a diiunctional monohydric phenol and furfural; said resin beingformed in the substantial absence of tritunctional phenols; said phenolbeing of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in the 2,4,6 position; said oxyethylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (C2H4O)1r; wherein nis a 20 numeral varying from 1 to 20; with the proviso that at least 2moles of ethylene oxide be introduced for each phenolic nucleus; andwith the final proviso that the hydrophile properties of saidoxyethylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

3. The process of claim 2, wherein R is an amyl radical.

4. The process of claim 2, wherein R radical.

5. The process of claim 2, wherein R is a nonyl radical.

is an octyl MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in th file ofthis patent: l

- UNITED STATES PATENTS De Groote et a1 Mar.-7,- 1950

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER,INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETICPRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENEOXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASSCONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDEAND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE,ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, LOW-STAGE PHENOL-FURFURALRESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONALMONOHYDRIC PHENOL AND FURFURAL; SAID RESIN BEING FORMED IN THESUBSTANTAIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THEFORMULA: